2-amino-7-heterocyclicaminothioxanthenes



PatentedApr. 15, 1952 Z-eAMINO-'Z-HETEROCYCLICAMINO- THIOXANTHENES 'EdwardDelbert Amstutz, Bethlehem, Pa assignor to The Wm. S. Men-ell Company, Cincinnati, Ohio, a corporation of Delaware No Drawing. Original application July 23, 1946, Serial No. 685,787. Divided and this application December 6, 1950, Serial No. 199,585

4 Claims.

The present invention relates to new chemical compounds and more particularly to 2-amino- 7(heterocyclic) aminothioxanthone dioxide and 2 amino 7(heterocyclic) aminothioxanthenol dioxide. These compounds characterized by an fiuxing begins. After 2 /2 hours the mixture is cooled, the white precipitate is filtered off,

anhydride.

aminophenyl group linked to a heterocyclic substituted aminophenyl group by a carbonyl or hydroxymethylene group and a sulfone (S02) group along with amino derivatives of the same are of value for combating bacterial infections. The compounds may be represented by the following formula:

where X represents a carbonyl or hydroxymethylene group, and R a heterocyclic group selected from the group consisting of pyridyl, pyrimidyl and thiazolyl.

EXAMPLE I p- Iod othiophenol (0.27 mole) is condensed with -nitro-2-chlorobenza1dehyde (0.26 mole) by refluxing in an atmosphere of nitrogen for 2 hours with-sodium bicarbonate (0.27 mole) in 870 m1. of 65% alcohol. The yellow precipitate is removed from the cooled mixture by filtration and iswashedwith alcohol and water and recrystallized from glacial acetic acid (800 ml.).

(b) Cyclization of 5-1'litW-2-(p-iodothiophenoxy) benzaldehyde 5 nitro-2-(p-iodothiophenoxy) benzaldehyde (0.296 mole) is dissolved in cold sulfuric acid washed, dried and digested twice with acetic 2-nitro-7-iodothioxanthone dioxide is obtained as an almost colorless crystalline powder.

(11) 2-amino-7-iodothio.mnthone dioxide 2 nitro 7 iodothioxanthone dioxide (0.28 mole) is suspended in glacial acetic acid (400 ml.) and is reduced at 85 C. by a solution of stannous chloride dihydrate (1.07 moles) in acetic acid (1200 ml.) saturated with gaseous hydrogen chloride. After cooling, the creamcolored precipitate is separated by filtrat'pn and is thoroughly digested with cold water to decompose the tin complex. The resultant yellow I precipitateis collected, washed and dried. It is a bright yellow powder.

(1140 ml.) and the dark red solution is poured (c) Z-nitro-7-iodothiomanthone dioride The mixture from step (b) is transferred to a flask containing 1500 ml. of glacial acetic acid, and chromium trioxide (1.25 moles) is added.

The mixture is heated very carefully until re- (4?) 2-amzno-7-(2-pyrimidyl) aminothioxanthone dioxide A mixture of 2-amino-'Z-iodothioxanthone dioxide (0.013 mole), 2-aminopyrimidine (0.16 mole), finely powdered potassium carbonate (0.015 mole) and a trace of copper powder is heated on an oil bath at 195 to 205 C. for about minutes under nitrogen. The cold reaction mixture is pulverized, extracted with cold water, and the residue is taken up in 5 normal nitric acid. The acid solution is filtered and then made alkaline by the addition of aqueous potassium hydroxide. The yellow precipitate is collected, washed and dried to give the 2-amino-7-(2- pyrimidyl) aminothioxanthone dioxide. The compound melts at 317-320 C. with decomposition. I

EXAMPLE II 2-AMINO-7-(2-PYRIMIDYL) AMINOTHIOXANTHENOL DIOXIDE 2-amino-7-(2-pyrimidyl) aminothioxanthone dioxide is reduced by means of zinc dust in boiling acetic acid to yield the corresponding thioxanthenol dioxide derivative.

By the method of Examples Nos. I and II, a

.wide range of heterocyclic derivatives of 2,7-

diaminothioxanthone dioxide and 2,7-diaminothioxanthenol dioxide may be prepared by condensing the 2-amino-7-iodo compound with the desired 2-amino-heterocyclic compound. Z-amino substituted heterocycles containing nitrogen or both nitrogen and sulfur in the ring may be employed, including such compounds as 2-aminopyridine, 2-aminothiazole, 2-amino-4- methyl thiazole, etc. Typical products are 2 amino-'I-[2-(4-methy1) thiazolyll aminothioxanthone dioxide and 2-amino-7-(2-thiazolyl) aminothioxanthone dioxide. The corresponding thioxanthenol dioxide compounds may be prepared by reduction of the thioxanthone dioxide analogues, or may be prepared by the halogenaminoheterocycle condensation of Example No. I.

The present application is a division of my prior application Serial No. 685,787 filed July 23, 1946, now abandoned.

I claim:

1. A compound represented by the formula X H1N- NHR where X is a radical selected from the group consisting of carbonyl and hydroxymethylene, and R is a heterocyclic radical selected from the group consisting of pyridyl, pyrimidyl and thiazolyl.

2; The compound, 2-amino-7-(2-pyrimidyl) aminothioxanthone dioxide.

3. The compound, 2-amino-7-(2-pyrimidyl) aminothioxanthenol dioxide.

4. The compound, 2-amino-7-(2-thiazolyl) aminothioxanthone dioxide.

EDWARD DELBERT AMSTUTZ.

No references cited. 

1. A COMPOUND REPRESENTED BY THE FORMULA 